Azo dyestuff insoluble in water



1 p UNITED STATES PATENT nnwm norrn AND Enwm minute, or

ASSIGNORS TO GENERAL AN'ILINE WOR TION OF DELAWARE OFFICE- FRANKFORT-ON-MAIN-HOCHST, GERMANY,

KS, INC., 01? NEW YORK, N. Y., AGOBPORA- '1 Azo DYES'IUFF' INSOLULBLEV IN WATER 1 No Drawing. Application filed September 13, 1929,

The present invention relates toblue to violet-blue water-insoluble azo dyestuffs; it is a continuation-impart application to our U. SLPatent No. 1,745,676.

We have found that dyestuifs of valuable dyeing properties and yielding blue to v10- let tints are obtainable by coupling with a 2.3-hydroxynaphthoylarylamine a' diazo compound ofa compound of the following general formula:

wherein R and R represent benzene nuclei at least one hydrogen atom in the two benzene nuclei being substituted by a substituent of the group consisting of acylamino, aryloxy, alkylthio, cyano, nitro, a carboxylic acid ester, carboxylic acid arylamido group, ahydrogenated aryl residue and an arylsulfo group, whereas the other hydrogen atoms of the benzene nuclei may be substituted by any monovalent substituent- In order to obtain water-insoluble dyestuflfs it is, of course, to be understood that such substituents as are capable of rendering the final products water-soluble are to be excluded. Such groups are, for instance, sulfonic and carboxylic acid groups.

The shades are varying within wide limits; reddish-violet to deep blackish-blue tints are obtained according to the selection of the components. 1 V

The dyestufis obtainable according to the present invention correspond to the following formula:

Rg.NH-R;N=N

. VH0 CONlI-aryl wherein R and R represent benzene nuclei at least one hydrogen; atom in the two benzene nucle being substituted by a subst t uent of the group consisting of acylamino,

Seria1 No..392,486,' andin Germany March fl, 1927.

aryloxy, 'alkylthio, cyano', nitro, a. carboxylic acid ester, carboxylic acid arylamido group, a hydrogenated aryl residue and an aryl'sulfo group, Whereas the other "hydrogen atoms of the benzene nuclei may be sub stituted by any inonovalent substituent, it being understood that such groups as are capable of rendering the final product watersoluble are excluded. l T

The following examples serve to illustrate our invention, but they are not intendedto limit it thereto; .the parts being by. Weight:

(1) 2.8 grams of 4-amino-dt-phenoxydiphenylamine are diazotized in, the usual manner with an excess of hydrochloricacid and sodium nitrite. The diazo solution which has been filtered, if necessary, and made up with cold water to 1 liter, is rendered neutral or nearly alkaline with bicarbonate and in thissolution there are dyed grams of cotton yarn which have been treated with "a grounding liquor containing 3 grams of 2.3-hydroxynaphthoic acid-orthotoluiclide, 12 grams of sodium Turkey red oil of 50per cent strength, 9 grams of caustic soda solution of 28 per cent strength, 6 grams of formaldehyde of 40; per cent strength in 1000 cc. of liquid. After the development the material is wrung out, thoroughly washed and soaped in a hot solution.

Diazo component Grounding liquor Dyeing 2.3-hydroxynaphthoyl 4 amino 2 cal-boxy mo 4 chloro 1 Reddish-blue thyl 2 chloro 4 methyl aniline diphenylamine 4 amino 2 carboxyethyldi- -1-aniline Very dark vio "phenylamine e t. 4: amino 4 cyanodiphenyl- 2' methyl 1 Reddish-blue amine aniline 4 amino 4 nitrodiphenyl- 2' methyl 1 Very dark vioamine aniline let. 4 amino 4 hexahydro 2 methyl 4 Reddish-blue phenyldiphenylamine chloro-1'-aniline 4 amino 4' acetylaminodi- 2 methyl l Reddish-bluo phenylamine v e aniline 4 amino 4 benzoylamino- 2 methyl 4 Middle blue diphenylamine chloro-1-aniline v 4 amino 2 carboxylic acid -1'-aniline v Reddish-blue anilidediphenylamine 4 amino 4 methyl 2 carbeta naphthyl Dark navyboxylic acidanilid di amine blue 'phenylamine V 4 amino 2 (para toluol -1'-aniline Reddish violet sulfonyD-diphenylamine v ethylthio 4 aminodi- -1-aniline Blue cphe'nylamine 4-amino-diphenylamine 4'1 chloro 2 Middle blue.

7 methyl-1-aniline strength. After the de elopment, the yarn is wrung out, well washed and treated in a hot soap bath. The dyeing thus obtained has a reddish-blue shade.

The following examples serve to furthermore illustrate the invention:

vary from reddish-violet to deep'blackishblue.

2. As new products, the dyestuffs of the following general formula:

Instead of'producing the dyestuffs on the fiber as indicated in the preceding examples they can also be produced in substance or on any of the usual substrata which are adapted for the production of lakes and isolated in a suitable manner.

Since the object of the present invention 'is to provide dyestuffs of good fastness properties, which dyestufis are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims contain no substituents as are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs to alkalies. are, for instance, the sulfonic acid and the carboxylic acid group.

' We claim: V

' 1. As new products, the dyestuffs of the following general formula:

the, group consisting of acylamino, aryloxy, alkylthio, cyano, nitro, a carboxylic acid ester, oarboxylic acid arylamido group, a hydrogenated aryl residue and an arylsulfo group, whereas the other hydrogen atoms of the benzene nuclei may be substituted by halogen, alkyl or alkoxy, which dyestuffs are insoluble in waterand yield when produced on the fiber dyeings, the shades of which of which vary from Substituents of this kind Qik g C 00-alkyl n OO-NH-aryl wherein thebenzene nucleus R may be substituted by halogen or alkyl, which dyestufis'are insoluble in water and yield when produced on the fiber dyeings, the shades reddish-violet to deep blackislrblue.

V 3. As anew product, the dyestuff of the following probable formula:

I L ""HQ I CIOHN OO Yielding When, produced on the fiber medium blue shades; p

4, As a new product, the dyestuff "of the following probable formulae z yielding when produced onithe fiber very dark violet shades 5. As new products, the dyestuffs of the following general'formula: V

wherein R stands fora radicalof the benzene orv naphthalene series,' which dyestuffs, are insoluble in water and yield when produced on the fiber dyeings the shades of which vary from violet to deep-blue.

' 6. As new products, the dyestuffs of the following general formula:

ONE;

wherein stands for a I benzene radical which'may be substituted by halogen, alkyl or alkoxy, which dyestuffs are insoluble in l OOCH:

water and yield when produced on the fiber 10. Fiber dyed with the dyestufi's as dyeings the shades of which vary from yiolet claimed in claim 6.

to deep-blue. 11. Fiber dyed with the dyestufi as claimed 7. As new products, the dyestuffs of the in claim 7. following general formula:

OO-NHG 12. Fiber dyed with the in claim 8.

COOCH:

wherein Z stands for hydrogen, a CH or'a OCH group, which dyestuffs, are insoluble in water and yield when produced on the fiber dyeings the shades of which Vary from reddish-blue to deep-blue.

8. As a new product, the dyestuff of th following general formula:

claimed in claim 1.

claimed in claim 2.

OCH;

which dyestufl", is insoluble in water and yields when produced on the fiber reddjshclaimed in claim 3. blue dyeings. 16. Fiber dyed with the dyestufi as 9. Fiber dyed with the 'dyestufi's as claimed in claim 4.

' ERWIN HOFFA.

claimed in claim 5..

ERWIN TI-IOMA.

dyestufi as claimed 13. Fiber dyed with the dyestufi's as 14. Fiber dyed with the dyestuffs as 15; Fiber dyed with ,the dyestufl's as. 

